Single layer lead iodide: Computational exploration of structural, electronic and optical properties, strain induced band modulation and the role of spin-orbital-coupling

Graphitic like layered materials exhibit intriguing electronic structures and thus the search for new types of two-dimensional (2D) monolayer materials is of great interest for developing novel nano-devices. By using density functional theory (DFT) method, here we for the first time investigate the structure, stability, electronic and optical properties of monolayer lead iodide (PbI2). The stability of PbI2 monolayer is first confirmed by phonon dispersion calculation. Compared to the calculation using generalized gradient approximation, screened hybrid functional and spin–orbit coupling effects can not only predicts an accurate bandgap (2.63 eV), but also the correct position of valence and conduction band edges. The biaxial strain can tune its bandgap size in a wide range from 1 eV to 3 eV, which can be understood by the strain induced uniformly change of electric field between Pb and I atomic layer. The calculated imaginary part of the dielectric function of 2D graphene/PbI2 van der Waals type hetero-structure shows significant red shift of absorption edge compared to that of a pure monolayer PbI2. Our findings highlight a new interesting 2D material with potential applications in nanoelectronics and optoelectronics.

Mapping bound plasmon propagation on a nanoscale stripe waveguide using quantum dots: Influence of spacer layer thickness

In this paper we image the highly confined long range plasmons of a nanoscale metal stripe waveguide using quantum emitters. Plasmons were excited using a highly focused 633 nm laser beam and a specially designed grating structure to provide stronger incoupling to the desired mode. A homogeneous thin layer of quantum dots was used to image the near field intensity of the propagating plasmons on the waveguide. We observed that the photoluminescence is quenched when the QD to metal surface distance is less than 10 nm. The optimised spacer layer thickness for the stripe waveguides was found to be around 20 nm. Authors believe that the findings of this paper prove beneficial for the development of plasmonic devices utilising stripe waveguides.

Synthesis and properties of fullerene C60 and C70 spin probes containing isoindoline nitroxides

Three fullerene isoindoline nitroxides N-methyl-3,4-fulleropyrrolidine-2-spiro-5′- (1′,1′,3′,3′-tetramethylisoindolin-2′-yloxyl), (C60-(TMIO)m, and C70-(TMIO)n) were synthesized by the covalent bonding of 5-formyl-1,1,3,3-tetramethyl isoindolin-2-yloxyl to the fullerenes C60 and C70. Significantly, the X-ray photoelectron spectra indicated the characteristic N 1s signals of NO. at 402 eV. The atomic force microscope morphologies showed that the average particle sizes of C60-(TMIO)m and C70-(TMIO)n were 38 and 15 nm. The electrochemical experiments indicated that fullerene bound isoindoline nitroxides retained similar electrochemical properties and redox reaction mechanisms as the parent nitroxides. The electron paramagnetic resonance spectra of the fullerene isoindoline nitroxides all exhibited the hyperfine splittings and characteristic spectra of tetramethyl isoindoline nitroxides, with typical nitroxide g-values and nitrogen isotropic hyperfine coupling constants. Therefore, these fullerene isoindoline nitroxides may be considered as potential candidates for novel biological spin probes using electron paramagnetic resonance spectroscopy.

A rapid and label-free dual detection of Hg (II) and cysteine with the use of fluorescence switching of graphene quantum dots

A simple and rapid method of analysis for mercury ions (Hg2+) and cysteine (Cys) was developed with the use of graphene quantum dots (GQDs) as a fluorescent probe. In the presence of GQDs, Hg2+ cations are absorbed on their negatively charged surface by means of electrostatic interactions. Thus, the fluorescence (FL) of the GQDs would be significantly quenched as a result of the FL charge transfer, e.g. 92% quenching at 450 nm occurs for a 5 μmol L−1 Hg2+ solution. However, when Cys was added, a significant FL enhancement was observed (510% at 450 nm for a 8.0 μmol L−1 Cys solution), and Hg2+ combined with Cys rather than with the GQDs in an aqueous solution. This occurred because a strong metalsingle bondthiol bond formed, displacing the weak electrostatic interactions, and this resulted in an FL enhancement of the GQDs. The limits of detection (LOD) for Hg2+ and Cys were 0.439 nmol L−1 and 4.5 nmol L−1, respectively. Also, this method was used successfully to analyze Hg2+ and Cys in spiked water samples.

TMIO-pyrimid hybrids are profluorescent, site-directed spin labels for nucleic acids

We report the synthesis of a new class of molecules which are hybrids of long-lived tetramethylisoindolinoxyl (TMIO) radicals and the pyrido[1,2-a]benzimidazole (PyrImid) scaffold. These compounds represent a new lead for noncovalently binding nucleic acid probes, as they interact with nucleic acids with previously unreported C (DNA) and C/U (RNA) complementarity, which can be detected by electron paramagnetic resonance (EPR) techniques. They also have promising properties for fluorimetric analysis, as their fluorescent spin-quenched derivatives exhibit a significant Stokes shift

Optimizing the quantum dot: Plasmon interaction in a nano gap waveguide

Spontaneous emission (SE) of a Quantum emitter depends mainly on the transmission strength between the upper and lower energy levels as well as the Local Density of States (LDOS)[1]. When a QD is placed in near a plasmon waveguide, LDOS of the QD is increased due to addition of the non-radiative decay and a plasmonic decay channel to free space emission[2-4]. The slow velocity and dramatic concentration of the electric field of the plasmon can capture majority of the SE into guided plasmon mode (Гpl ). This paper focused on studying the effect of waveguide height on the efficiency of coupling QD decay into plasmon mode using a numerical model based on finite elemental method (FEM). Symmetric gap waveguide considered in this paper support single mode and QD as a dipole emitter. 2D simulation models are done to find normalized Гpl and 3D models are used to find probability of SE decaying into plasmon mode ( β) including all three decay channels. It is found out that changing gap height can increase QD-plasmon coupling, by up to a factor of 5 and optimally placed QD up to a factor of 8. To make the paper more realistic we briefly studied the effect of sharpness of the waveguide edge on SE emission into guided plasmon mode. Preliminary nano gap waveguide fabrication and testing are already underway. Authors expect to compare the theoretical results with experimental outcomes in the future

Graphene quantum dots and the resonance light scattering technique for trace analysis of phenol in different water samples

A novel, highly selective resonance light scattering (RLS) method was researched and developed for the analysis of phenol in different types of industrial water. An important aspect of the method involved the use of graphene quantum dots (GQDs), which were initially obtained from the pyrolysis of citric acid dissolved in aqueous solutions. The GQDs in the presence of horseradish peroxidase (HRP) and H2O2 were found to react quantitatively with phenol such that the RLS spectral band (310 nm) was quantitatively enhanced as a consequence of the interaction between the GQDs and the quinone formed in the above reaction. It was demonstrated that the novel analytical method had better selectivity and sensitivity for the determination of phenol in water as compared to other analytical methods found in the literature. Thus, trace amounts of phenol were detected over the linear ranges of 6.00×10−8–2.16×10−6 M and 2.40×10−6–2.88×10−5 M with a detection limit of 2.20×10−8 M. In addition, three different spiked waste water samples and two untreated lake water samples were analysed for phenol. Satisfactory results were obtained with the use of the novel, sensitive and rapid RLS method.

A novel fluorescent probe involving a graphene quantum dot-enzyme hybrid system for the analysis of hydroquinone in the presence of toxic resorcinol and catechol

An efficient method for the analysis of hydroquinone at trace levels in water samples has been developed in the form of a fluorescent probe based on graphene quantum dots (GQDs). The analytical variable, fluorescence quenching, was generated from the formation of benzoquinone intermediates, which formed during the catalytic oxidation of hydroquinone by horseradish peroxidase (HRP). In general, the reaction mechanism involved hydroquinone, as an electron acceptor, which affected the surface state of GQDs via an electron transfer effect. The water-soluble GQDs were directly prepared by the pyrolysis of citric acid and with the use of the mentioned hybrid enzyme system, the detection limit for hydroquinone was as low as 8.4 × 10−8 M. Furthermore, this analysis was almost unaffected by other phenol and quinine compounds, such as phenol, resorcinol and other quinines, and therefore, the developed GQD method produced satisfactory results for the analysis of hydroquinone in several different lake water samples.

Applying POVM to model non-orthogonality in quantum cognition

Much of the work currently occurring in the field of Quantum Interaction (QI) relies upon Projective Measurement. This is perhaps not optimal, cognitive states are not nearly as well behaved as standard quantum mechanical systems; they exhibit violations of repeatability, and the operators that we use to describe measurements do not appear to be naturally orthogonal in cognitive systems. Here we attempt to map the formalism of Positive Operator Valued Measure (POVM) theory into the domain of semantic memory, showing how it might be used to construct Bell-type inequalities.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

The role of lysine-41 in RNase A catalysis - A quantum chemical study on the active site ligand complex

Several mechanisms have been proposed to explain the action of enzymes at the atomic level. Among them, the recent proposals involving short hydrogen bonds as a step in catalysis by Gerlt and Gassman [1] and proton transfer through low barrier hydrogen bonds (LBHBs) [2, 3] have attracted attention. There are several limitations to experimentally testing such hypotheses, Recent developments in computational methods facilitate the study of active site-ligand complexes to high levels of accuracy, Our previous studies, which involved the docking of the dinucleotide substrate UpA to the active site of RNase A [4, 5], enabled us to obtain a realistic model of the ligand-bound active site of RNase A. From these studies, based on empirical potential functions, we were able to obtain the molecular dynamics averaged coordinates of RNase A, bound to the ligand UpA. A quantum mechanical study is required to investigate the catalytic process which involves the cleavage and formation of covalent bonds. In the present study, we have investigated the strengths of some of the hydrogen bonds between the active site residues of RNase A and UpA at the ab initio quantum chemical level using the molecular dynamics averaged coordinates as the starting point. The 49 atom system and other model systems were optimized at the 3-21G level and the energies of the optimized systems were obtained at the 6-31G* level. The results clearly indicate the strengthening of hydrogen bonds between neutral residues due to the presence of charged species at appropriate positions. Such a strengthening manifests itself in the form of short hydrogen bonds and a low barrier for proton transfer. In the present study, the proton transfer between the 2'-OH of ribose (from the substrate) and the imidazole group from the H12 of RNase A is influenced by K41, which plays a crucial role in strengthening the neutral hydrogen bond, reducing the barrier for proton transfer.

Unoccupied electronic states in NiS2-xSex across the metal-insulator transition

We investigate the evolution of the electronic structure across the insulator-metal transition in NiS2-xSex with changing composition, but in the absence of any structural or magnetic changes. A comparison of the inverse photoemission spectra with band-structure calculations establishes the importance of correlation effects in these systems. Systematic changes in the spectral distribution establish the persistence of the upper Hubbard band well into the metallic regime, with the insulator-to-metal transition being driven by a transfer of spectral weight from the Hubbard band to states close to the Fermi energy.

Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Structural and optical investigation of semiconductor CdSe/CdS core-shell quantum dot thin films

Highly luminescent CdSe/CdS core-shell nanocrystals have been assembled on indium tin oxide (ITO) coated glass substrates using a wet synthesis route. The physical properties of the quantum dots (QD) have been investigated using X-ray diffraction, transmission electron microscopy and optical absorption spectroscopy techniques. These quantum dots showed a strong enhancement in the near band edge absorption. The in situ luminescence behavior has been interpreted in the light of the quantum confinement effect and induced strain in the core-shell structure.

Working group report: Quantum chromodynamics sub-group

This is the report of the QCD working sub-group at the Tenth Workshop on High Energy Physics Phenomenology (WHEPP-X).